Phenoxyphenoxy unsaturated derivatives and herbicidal composition

ABSTRACT

A herbicidal composition which comprises a phenoxyphenoxy unsaturated derivative having the formula:   &lt;IMAGE&gt;   wherein X represents a halogen atom or CF3; Y represents a hydrogen atom or a halogen atom; and Z represents -COOR, -COR&#39;&#39;, -COOH, -CH2 OH, or -CH2OR&#39;&#39;&#39;.

This is a division of application Ser. No. 6,387, filed Jan. 25, 1979and now U.S. Pat. No. 4,263,040.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to phenoxyphenoxy unsaturated derivativeshaving the formula ##STR2## wherein X represents a halogen atom or CF₃ ;Y represents a hydrogen atom or a halogen atom; and Z represents --COOR,--COSR', --COR", --COOH, --CH₂ OH or --CH₂ OR'" and R representscyanoethyl, dialkylaminoethyl, alkoxyalkyl, benzyl, dialkylbenzyl,alkylbenzyl, halobenzyl, pyridinomethyl, furfuryl, cycloalkyl,methylcycloalkyl, phenyl, halophenyl, methyl phenyl, alkoxy alkyleneoxyalkyl, methoxymethylbutyl group, a metal atom, amino, alkylamino orarylamino group; and when X is a halogen atom, R can be an alkyl,haloalkyl, alkenyl, haloalkenyl, alkynyl or hydrogen atom group; and R'represents alkyl, phenyl, chlorophenyl, chlorobenzyl or methoxy benzylgroup, and R" represents, amino, alkylamino, dialkylamino, phenylaminoor phenylamino group which may be substituted by halo or alkyl group,and R'" represents an acetyl, chloroacetyl, benzoyl, ethoxycarbonyl,methylcarbamoyl or phenylcarbamoyl group.

The present invention also relates to herbicidal compositions comprisingsaid compound as an active ingredient.

Recently, many herbicides have been proposed and practically used tocontribute for elimination of agricultural labor.

Thus, various problems on herbicidal effects and safety of theherbicides have been found in the practical applications.

It has been required to find improved herbicides which have no adverseeffect to the object plants and effective to noxious weeds in a smalldose of the active ingredient and significantly safe without anyenvironmental pollution.

The inventors have synthesized various phenoxyphenoxy unsaturatedderivatives so as to find satisfactory herbicides and have studiedherbicidal effects thereof.

The novel compounds of phenoxyphenoxy unsaturated derivatives having theformula (I) of the present invention have superior herbicidal activityto gramineous weeds such as barnyard grass, crab grass and Johnson grassincomparison with the compounds described in Japanese Unexamined PatentPublication No. 33637/1977 such as methyl4-[4-(4 trifluoromethylphenoxy)phenoxy] crotonate, ethyl 4-[4-(4-trifluoromethyl-2-chlorophenoxy)phenoxy] crotonate, ethyl γ-[4-(4-trifluoromethylphenoxy) phenoxy]valerylate and ethyl γ-[4-(4-trifluoromethyl-2-chlorophenoxy) phenoxy]valerylate. The novel compounds of the present invention have superiorresidual activity in a soil treatment in comparison withα-[4-(4-trifluoromethylphenoxy) phenoxy] propionic acid derivativesdisclosed in Japanese Unexamined Patent Publication No. 12924/1976.

The novel compounds of the present invention have superior herbicidalactivities in comparison with dimethylammonium γ-[4-(4-chlorophenoxy)phenoxy] valerianate, and sodium γ-[4-(2',4'-dichlorophenoxy) phenoxy]valerianate disclosed in Japanese Unexamined Patent Publication No.131540/1977; and ethyl α-[4-(4'-chlorophenoxy) phenoxy] propionate,methyl-α-[4-(2',4'-dichlorophenoxy) phenoxy] propionate, sodiumα-[4-(4'-bromophenoxy) phenoxy] propionate and potassiumα-[4-(4'-chlorophenoxy) phenoxy] propionate disclosed in JapaneseUnexamined Patent Publication No. 54525/1974 and sodiumα-[4-(2-chloro-4'-bromophenoxy) phenoxy propionate and dimethylammoniumα-2'-chloro-4'-bromophenoxy phenoxy propionate, disclosed in JapaneseUnexamined Patent Publication No. 89628/1977.

The novel compounds of the present invention also have excellent effectssuch as a long suppression of weeds in later emergence; a longsuppression of recovery from an incomplete suppression of weeds in afoliage treatment; growth control of grown weeds and excellent stabilityto the factors for varying the activity caused by rainfall, atmosphericmoisture and high temperature to impart stable activity.

The novel compounds of the present invention have methyl group atγ-position of the phenoxyphenoxy unsaturated compounds (I) whereby thespecial herbicidal effect especially, significant herbicidal effect togramineous weeds such as Johnson grass, dent foxtail, barnyard grass andlarge crab grass can be imparted.

The novel compounds of the present invention have significantselectivity without phytotoxicity to broad leaf crop plants such asradish, soybean, peanut, cotton, flax, beet, pimento and sunflower, butcompletely control gramineous weeds barnyard grass, large crab grass,Johnson grass, wild sorghum, quack grass, dent foxtail and paspalumgrass.

The novel compounds of the present invention can be applied asherbicides by desirable methods in every season such as the soiltreatment and the foliage treatment in post-emergence and pre-emergence.

The significant characteristics of the novel compounds are to havesignificant herbicidal effect in the foliage treatment, for example, tocompletely control Johnson grass in 5 leaf-stage or more.

Typical gramineous weeds which are effectively controlled by theherbicides of the present invention are as follows: Johnson grass, quackgrass, para-grass, southern sandbar, finger grass, bermuda grass,crowfoot grass, large crab grass, crab grass, barnyard grass, junglerice, cattail grass, goose grass, cogon grass, wrinkle grass, southerncut grass, Bearded splangle top, red splangle top, mexican splangle top,brown top panicum, sour paspalum, water paspalum, natal grass, raoulgrass, green foxtail, bristly foxtail, yellow foxtail.

The phenoxyphenoxy unsaturated derivatives having the formula (I) can beproduced by the following processes.

(1) The phenoxyphenoxy unsaturated derivatives having the formula (I)##STR3## (X, Y and Z are defined above) can be produced by reacting anunsaturated halide having the formula ##STR4## (Z' is Z defined above ora group convertible to Z and Hal is a halogen atom) with a phenoxyphenolhaving the formula ##STR5## (X and Y are defined above) in the presenceof a base at 0° to 150° C. for 1 to 20 hours and if necessary,converting Z' into Z. In the formula, the groups convertible to Zinclude cyano, halogen and other functional groups.

Suitable bases include alkali metal hydroxides such as sodium hydroxideor potassium hydroxide; alkali metal carbonates such as sodiumcarbonate, potassium carbonate, sodium bicarbonate; alcoholates such assodium ethylate and tertiary amines such as triethylamine, dimethylaniline or pyridine, etc.

Suitable reaction media include water, acetone, methylethyl ketone,methanol, isopropanol, butanol, dimethylformamide, dimethylsulfoxide,tetrahydrofuran, benzene, toluene, xylene, chlorobenzene, chloroform,carbon tetrachloride, dichloroethane, etc.

The resulting compound can be converted into a desired phenoxyphenoxyunsaturated derivative by the following processes.

The object compounds of phenoxyphenoxy unsaturated derivatives (I) canbe produced directly reacting a phenoxyphenol having the formula##STR6## with a halopentenoic compound or a halopentenol compound havingthe formula ##STR7## in the presence of a base in suitable solvent at 0°to 150° C. for 1 to 20 hours.

The object compounds of phenoxyphenoxy unsaturated acid esters havingthe formula ##STR8## can be produced by reacting the phenoxyphenolhaving the formula ##STR9## with a halopentenoic acid to produce aphenoxyphenoxy unsaturated acid having the formula ##STR10## and then,reacting the corresponding compound having the formula ROH with thephenoxyphenoxy unsaturated acid (IV) or its acid halide having theformula ##STR11## in suitable solvent or without a solvent at 0° to 150°C. for 1 to 20 hours.

The phenoxyphenoxy unsaturated acid halide (IV') can be easily obtainedby reacting a halogenating agent such as thionyl chloride, andphosphorus trihalides with the phenoxyphenoxy unsaturated acid (IV).

The object compounds of phenoxyphenoxy unsaturated acid amides havingthe formula ##STR12## can be also produced by reacting thephenoxyphenoxy unsaturated acid (IV) or its acid halide (IV') with thecorresponding amine or ammonia in suitable inert solvent with or withoutan alcoholate, sodium amide or sodium hydride, at 0° to 150° C. for 1 to20 hours.

The object compounds of phenoxyphenoxy unsaturated acid thiol estershaving the formula ##STR13## can be also produced by reacting thephenoxyphenoxy unsaturated acid (IV) or its acid halide (IV') with thecorresponding mercaptan in the presence of a base as adehydrohalogenation agent in suitable inert solvent or without a solventat -10° to 150° C. for 1 to 20 hours.

The object compounds of phenoxyphenoxy pentenols having the formula##STR14## can be produced by hydrogenating the phenoxyphenoxyunsaturated acid (IV) or its acid halide (IV') or its ester, with areducing agent such as sodium boron hydride and aluminum lithiumhydride, in suitable insert solvent at -20° to 100° C. for 1 to 20hours.

The object compounds of phenoxyphenoxy pentenol derivatives having theformula ##STR15## can be also produced by reacting the phenoxyphenoxypentenol with a compound having the formula R"' OH or R"'NH₂ in suitableinert solvent at 0° to 150° C. for 1 to 20 hours.

These object compounds are produced by the main reaction of thephenoxyphenol (III) with the unsaturated halide (II) and if necessary,converting the product into the object compound.

The following shows certain processes for converting the productobtained by the main reaction.

(a) The phenoxyphenoxy unsaturated derivatives having the formula (I)can be produced by reacting a phenoxyphenoxy unsaturated acid having theformula ##STR16## with a compound having the formula ROH (X, Y and R aredefined above) in the presence of a catalyst such as an aromaticsulfonic acid such as benzenesulfonic acid, toluenesulfonic acid orβ-naphthalenesulfonic acid; an anhydrous sulfate such as anhydrouscopper sulfate or anhydrous iron sulfate; phosphorus oxychloride,phosphoric acid anhydride, boron trifluoride or acidic ion-exchanger at20° to 150° C. or under refluxing for 1 to 20 hours.

(b) The phenoxyphenoxy unsaturated derivatives having the formula (I)can be produced by reacting a phenoxyphenoxy unsaturated acid having theformula ##STR17## with a base such as alkali metal hydroxides, alkalineearth metal hydroxides and organic bases e.g. amines and aminocompounds, in a reaction medium at 0° to 100° C. for 0.5 to 10 hours.

(c) The phenoxyphenoxy unsaturated derivatives having the formula (I)can be produced by reacting phenoxyphenoxy pentenoyl halide having theformula ##STR18## with a compound having the formula ROH, R'SH or R"H.(X, Y, R and Hal are defined above) in the absence ofdehydrohalogenating agent of a base in a reaction medium or excess ofthe compound having the formula ROH or without a reaction medium, at-10° to 150° C. for 1 to 20 hours.

Suitable dehydrogenhalide agents of inorganic or organic bases includealkali metal hydroxides such as sodium hydroxide or potassium hydroxide;alkali metal carbonates such as sodium carbonate, potassium carbonate orsodium bicarbonates; alcoholates such as sodium ethylate; and tertiaryamines such as triethyl amine, dimethyl aniline or pyridine.

Suitable reaction media include acetone, methyl ethyl ketone,dimethylformamide, dimethylsulfoxide, tetrahydrofuran, benzene, toluene,xylene, chlorobenzene, chloroform, carbon tetrachloride anddichloroethane.

The phenoxyphenoxy pentenoic halide (V) can be produced by reacting thephenoxyphenoxy unsaturated acid (IV) with thionyl chloride or phosphorustrihalide in a solvent.

(d) The phenoxyphenoxy pentenoate having the formula ##STR19## wherein Mis an alkali metal, an alkaline earth metal, a heavy metal or an aminogroup including an alkylamino and an arylamino group; can be easilyproduced by neutralizing the corresponding acid or acid halide with thecorresponding base.

The reaction is preferably carried out in a solvent at higher than roomtemperature.

(e) The phenoxyphenoxy pentenol derivatives having the formula ##STR20##wherein R represents hydrogen atom, an alkyl carbonyl, haloalkylcarbonyl, an aryl carbonyl, an alkylamino carbonyl or anarylaminocarbonyl group can be easily produced by reacting4-halogeno-2-pentenol or its ester with a phenoxyphenol having theformula ##STR21##

The reaction is preferably carried out in a solvent in the presence of abase.

When the phenoxyphenoxy pentenol (B═H) is produced, the product can beesterified to obtain the corresponding ester.

(f) The phenoxyphenoxy pentenols having the formula ##STR22## can beproduced by reducing a phenoxyphenoxy unsaturated derivative having theformula ##STR23## (A' is OR, or a halogen atom obtained in the processesof (a) (b) (c) (d) or (e) in the presence of a reducing agent such aslithium aluminum hydride and sodium boro hydride in a reaction medium at-20° to 100° C. for 1 to 20 hours.

If necessary, the resulting phenoxyphenoxy pentenol is esterifying withthe corresponding acid to obtain its esters.

Certain examples for producing the compounds by this process will bedescribed.

PREPARATION 1--1 Ethyl 4-[4(2,4-dichlorophenoxy) phenoxy](2)-pentenoate

In 100 ml of dimethylformamide, 25.5 g (0.1 mole) of4-(2,4-dichlorophenoxy) phenol was dissolved and 19.3 g (0.14 mole) ofsodium carbonate and 24.8 g (0.12 mole) of ethyl 4-bromo-2-pentenoatewere added. The mixture was stirred at 100° C. for 6 hours to reactthem. The reaction mixture was poured into water and the reactionproduct was extracted with dichloromethane. The dichloromethane phasewas washed with water, with a dilute hydrochloric acid and then, withwater and dehydrated over anhydrous sodium sulfate and dichloromethanewas distilled off and the residue was distilled in vacuum to obtain 32.5g (yield of 85.2%) of pale yellow viscous liquid having a boiling pointof 180° to 190° C./0.007 mmHg and N_(D) ²⁰ of 1.5566.

PREPARATION 1--2 Methyl 4-[4-(4-bromophenoxy) phenoxy](2)-pentenoate

A mixture of 73 g (0.2 mole) of 4[4-(4-bromophenoxy)phenoxy](2)-pentenoic acid, 200 ml of methanol and 10 g of conc.sulfuric acid was refluxed for 4 hours and about a half of methanol wasdistilled off and then, 300 ml of water was added to dilute it and theresulting oily product was extracted with ester and the ether phase wasdehydrated over anhydrous sodium sulfate and ether was distilled off toobtain 66 g (yield of 87.5%) a brown transparent viscous liquid andN_(D) ²⁰ :1.5822.

PREPARATION 1-3 Isopropyl 4-[4-(4-iodophenoxy) phenoxy](2)-pentenoate

In 70 ml of isopropyl alcohol, 22 g (0.05 mole) of ethyl4-[4-(4-iodiophenoxy) phenoxy]2-pentenoate and 3 g of sulfuric acid wereadded and the mixture was refluxed for 15 hours to react them, and about50 ml of isopropyl alcohol was distilled off and 150 ml of water wasadded and the resulting oily product was extracted with ether. The etherphase was washed with water and dehydrated over anhydrous sodium sulfateand ether was distilled off to obtain a dark brown viscous liquid havingN_(D) ²⁰ :1.5753 (yield of 74.0%).

PREPARATION 1-4 N-sec butyl 4-[4-(4-bromophenoxy)phenoxy](2)-pentenamide

In 100 ml of methanol, 18.9 g of methyl 4-[4-(4-bromophenoxy)phenoxy]2-pentenoate was dissolved and 20 ml of 4% an aqueous solutionof sec-butylamine was added to react them at room temperature for 4hours. After the reaction, water was added to precipitate crystals andthen, the product was recrystallized from methanol/water to obtain 15.8g (yield 75.5%) of brown color crystals having a melting point of 127°to 128° C.

PREPARATION 1-5 4-[4-(4-chlorophenoxy) phenoxy](2)-pentenamide

A mixture of 6.4 g (0.02 mole) of 4-[4-(4-chlorophenoxy)phenoxy]2-pentenoic acid and 30 ml of thionyl chloride was refluxed for6 hours.

Excess of thionyl chloride was removed from the reaction mixture and theresidue of the acyl chloride was dissolved in 20 ml of acetone and 50 mlof 5% ammonia water was added to react them at room temperature for 1hour and crystals were separated and washed with water andrecrystallized from water-ethanol to obtain 5.2 g (yield 81.8%) of paleyellow powdery crystals having a melting point of 135° to 137° C.

In accordance with the same process, Compounds No. 1-6, 12, 19, 20, 21and 27 were produced by using the corresponding amine and thecorresponding pentenoic acid.

PREPARATION 1-6 Methyl 4-[4-(4-bromophenoxy) phenoxy](2)-pentenoate

In 250 ml of anhydrous methanol, 37.0 g (0.1 mole) of4-[4-(4-bromophenoxy) phenoxy](2)-pentenoyl chloride was added undercooling and the mixture was stirred at room temperature for 2 hours andat 40° to 45° C. for 2 hours and excess of methyl alcohol was distilledoff to obtain 35.2 g (yield 93.0%) of brown transparent viscous liquidhaving N_(D) ²⁰ :1.5822.

In accordance with the same process, Compounds No. 1-3, 4, 5, 8, 9, 10,11, 14, 15, 16, 17, 22, 25 and 26 were produced by using thecorresponding alcohol and the corresponding acyl chloride.

PREPARATION 2-1 Ethyl4-[4-(4-bromo-2-chlorophenoxy)phenoxy](2)-pentenoate

In 60 ml of ethanol, 9.0 g (0.03 mole) of 4-(4-bromo-2-chlorophenoxy)phenol and 7.6 g (0.036 mole) of ethyl 4-bromo-2-penetenoate weredissolved and 4.6 g (0.033 mole) of potassium carbonate was added andthe mixture was refluxed for 3 hours to react them. The reaction productwas extracted with ether and the ether phase was washed with water anddehydrated over anhydrous sodium sulfate and ether was distilled off andlower boiling materials having boiling point of lower than 140° C./0.01mmHg were distilled off to obtain 11.7 g of an orange viscous liquidhaving N_(D) ²⁰ :1.5794. (yield: 91.5%).

PREPARATION 2--2 Isopropyl 4-[4-(2-chloro-4-bromo-phenoxy)phenoxy]-2-pentenoate

A mixture of 19.9 g (0.05 mole) of 4-[4-(2-chloro-4-bromophenoxy)phenoxy[(2)-pentenoic acid, 50 ml of isopropanol, 50 ml of benzene and 3g of conc. sulfuric acid was refluxed under removing water by a trap for5 hours. After the reaction, 100 ml of water was added and the benzenephase was washed sequentially with 5% aqueous solution of sodiumhydroxide, water, a dilute hydrochloric acid and water, and dehydratedover anhydrous sodium sulfate and benzene was distilled off to obtain17.9 g of an orange viscous liquid having N_(D) ²⁰ :1.5710. (yield:81.5%).

PREPARATION 2-3 2-Chloroethyl 4-[4-(2-chloro-4-bromophenoxy)phenoxy](2)-pentenoate

A mixture of 11.9 g (0.03 mole) of 4-[4-(2-chloro-4-bromophenoxy)phenoxy]2-pentenoic acid and 20 ml of thionyl chloride was refluxed for6 hours. Excess of thionyl chloride was distilled off from the reactionmixture and 20 ml of 2-chloroethanol was added to the residue of theacyl chloride, and the mixture was gradually heated to react them at 60°C. for 5 hours and excess of 2-chloroethanol was distilled off to obtain11.4 g of an orange viscous liquid having N_(D) ²⁰ :1.5902. (yield:89.0%).

PREPARATION 2-4 Allyl 4-[4-(2-chloro-4-bromophenoxy)phenoxy]2-pentenoate

In a mixture of 70 ml of benzene, 2.1 g (0.030 mole) of allyl alcoholand 2.6 g (0.033 mole) of pyridine, 12.5 g (0.03 mole) of[4-(2-chloro-4-bromophenoxy) phenoxy]2-pentenoic chloride obtained inthe previous Preparation was added to react them at room temperature.Water was added to the reaction mixture and the benzene phase was washedwith water and dehydrated over anhydrous sodium sulfate and benzene wasdistilled off to obtain 11.5 g of an orange viscous liquid having N_(D)²⁰ :1.5757 (yield 87.3%).

In accordance with the same process, Compounds No. 2-1, 2, 3, 5 and 6were produced by using the corresponding alcohol.

PREPARATION 3-1 4-[4-(4-clorophenoxy) phenoxy]2-pentenoic aciddimethylamine salt

In 15 ml of 10% dimethylamine aqueous solution, 7.0 g (0.02 mole) of4-[4-(4-chlorophenoxy) phenoxy]2-pentenoic acid was dissolved and then,excess of dimethylamine and water was removed by a rotary evaporator toobtain 6.5 g of an orange viscous liquid, (yield: 92.2%).

In accordance with the same process, Compound No. 3-5 was produced byusing the corresponding amine.

PREPARATION 4-1 Methoxyethyl 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoate

In 70 ml of ethanol, 10.2 g (0.04 mole) of 4-(trifluoromethylphenoxy)phenol and 11.4 g (0.048 mole) of methoxyethyl 4-bromo-2-pentenoate weredissolved and 6.1 g (0.044 mole) of potassium carbonate was added andthe mixture was refluxed for 4 hours to react them. The reaction mixturewas extracted with ether and the ether phase was washed with water anddehydrated over anhydrous sodium sulfate, and then, ether was distilledoff and lower boiling materials having boiling point of lower than 140°C./0.01 mmHg was distilled off to obtain 15.2 g of an orange viscousliquid having N_(D) ²⁰ :1.5156 (yield: 92.3%).

PREPARATION 4-2 Ethoxyethyl 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoate

A mixture of 17.7 g (0.05 mole) of 4-[4-(4-trifluoromethylphenoxy)phenoxy]2-pentenoic acid, 50 ml of ethyl cellosolve, 50 ml of benzeneand 3 g of conc. sulfuric acid was refluxed under removing water by atrap for 4 hours. After the reaction, 100 ml of benzene was added todilute the product and the benzene phase was washed with water anddehydrated over anhydrous sodium sulfate and then benzene was distilledoff and lower boiling materials having boiling point of lower than 140°C./0.01 mmHg were distilled off to obtain 17.9 g of an orange viscousliquid having N_(D) ²⁰ :1.5134 (yield: 84.4%).

PREPARATION 4-3 1-Methoxypropyl 4-[4-(4-bromo-2-clorophenoxy)phenoxy](2)-pentenoate

A mixture of 14.2 g of 4-[4-(4-bromo-2-chlorophenoxy)phenoxy]2-pentenoic acid and 25 ml of thionyl chloride was refluxed for6 hours to react them. Excess of thionyl chloride was distilled off fromthe reaction mixture and 15 ml of 2-methoxypropyl alcohol was added tothe residue of the acid chloride. After the addition, the mixture wasgradually heated to react them at 60° C. for 5 hours and excess of2-methoxypropyl alcohol was distilled off under a reduced pressure toobtain 17.2 g of an orange viscous liquid having N_(D) ²⁰ :1.5210(yield: 91.3%).

PREPARATION 4--4 n-Butoxyethyl 4-[4-(4-bromo-2-chlorophenoxy)phenoxy](2)-pentenoate

In a mixture of 70 ml of toluene, 4.7 g (0.04 mole) of n-butoxyethanoland 4.6 g (0.033 mole) of potassium carbonate, 12.5 g (0.03 mole) of4-[4-(4-bromo-2-chlorophenoxy) phenoxy] 2-pentenoyl chloride obtained inthe previous Preparation, was added and the mixture was gradually heatedat 50° to 60° C. for 1 hour. The toluene phase was sequentially washedwith water, 5% aqueous solution of sodium hydroxide and water anddehydrated over anhydrous sodium sulfate and then, toluene was distilledoff to obtain 13.7 g of an orange viscous liquid having N_(D) ²⁰ :1.5108(yield: 92.0%).

In accordance with the same process, Compounds No. 4-1, 2, 3, 4, 5, 6and 8 were produced by using the corresponding alcohol.

Preparation 4-5 Methoxymethyl 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)- pentenoate

In 100 ml of acetone, 11.2 g (0.03 mole) of sodium4-[4-(4-trifluoromethylphenoxy) phenoxy](2)-pentenoate was suspended,and then, 3.6 g (0.045 mole) of methoxymethyl chloride was added and themixture was stirred at room temperature for 3 hours and then, refluxedfor 8 hours to react them. After the reaction, the reaction product wasextracted with ether and the ether phase was sequentially washed withwater. 5% aqueous solution of sodium hydroxide and water and dehydratedover anhydrous sodium sulfate, and then, ether was distilled off andlower boiling materials having boiling point of lower than 140° C./0.01mmHg were distilled off in vacuum to obtain 8.7 g of an orange viscousliquid having N_(D) ²⁰ :1.5208 (yield: 77.6%).

PREPARATION 5-1 N,N-diethyl 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenamide

In 300 ml of acetone, 25.4 g (0.1 mole) of 4-(4-trifluoromethylphenoxy)phenol was dissolved and 19.3 g of sodium carbonate was added and 23.4 g(0.1 mole) of N,N-diethyl 4-bromo (2)-potenamide was added understirring and the mixture was stirred at 60° C. for 2 hours. The reactionmixture was poured into ice water and an oily product was extracted withether and the ether phase was washed with water and dehydrated and etherwas distilled off and the residue was distilled off in vacuum to obtain36.2 g of an orange viscous liquid having a boiling point of 190° to190° to 192° C./0.015 mmHg and N_(D) ²⁰ :1.5323 (yield: 89.2%).

PREPARATION 5-2 4-[4-(4-trifluoromethylphenoxy) phenoxy](2)-pentenamide

A mixture of 7.4 g (0.02 mole) of 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoic acid and 30 ml of thionyl chloride was refluxedfor 6 hours to react them. Excess of thionyl chloride was distilled offfrom the reaction mixture and the residue of the acyl halide wasdissolved in 20 ml of acetone and 50 ml of 5% ammonia water was added toreact them at room temperature for 1 hour.

The resulting precipitate was filtered and recrystallized fromwater-ethanol to obtain 5.7 g of white crystals having m.p. of 140° to142° C. (yield: 81.4%).

In accordance with the same process, Compounds No. 5--5 to 5-10 wereproduced by using the corresponding amine.

PREPARATION 6-1 Phenyl 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoate

In 50 ml of ethanol, 12.7 g (0.05 mole) of 4-(4-trifluoromethylphenoxy)phenol, 12.8 g (0.05 mole) of phenyl 4-bromo (2)-pentenoate and 7 g(0.05 mole) of anhydrous potassium carbonate were added and the mixturewas refluxed under stirring for 3 hours. After the reaction, thereaction mixture was poured into 200 ml of ice water and an oily productwas extracted with toluene and the toluene phase was sequentially washedwith 5% aqueous solution of sodium hydroxide, and water and dehydratedover anhydrous magnesium sulfate and toluene was distilled off under areduced pressure and the residue was heated at 110° C. under a reducedpressure 0.05 mmHg to obtain 19.5 g of a yellow viscous liquid havingN_(D) ²⁰ :1.5471 (yield: 91.1%).

PREPARATION 6-2 Dimethylaminoethyl 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoate

In 50 of benzene, 7.4 g (0.02 mole) of 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoyl chloride and 3.6 g (0.04 mole) ofdimethylaminoethanol were added and the mixture was heated at 50° C. for3 hours to react them. After the reaction, the benzene solution wassequentially washed with water, 5% aqueous solution of sodium carbonateand water and dehydrated over anhydrous sodium sulfate and benzene wasdistilled off and low boiling materials were distilled off at 115° C.under 0.095 mmHg to obtain 8.0 g of pale yellowish orange viscous liquidhaving N_(D) ²⁰ :1.5178 (yield 94.1%).

PREPARATION 6-3 3-Methoxy-3-methylbutyl 4[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoate

In 40 ml of benzene, 5.0 g (0.013 mole) of4-[4-(4-trifluoromethylphenoxy) phenoxy] (2)-pentenoyl chloride and 2.1g (0.018 mole) of 3-methoxy-3-methylbutanol were dissolved and themixture was refluxed for 6 hours under stirring. The reaction wasperformed under generating hydrogen chloride gas. The reaction mixturewas cooled and mixed with 100 ml of benzene and the benzene phase waswashed two times with 50 ml of saturated aqueous solution of sodiumbicarbonate and two times with water and dehydrated over anhydroussodium sulfate and benzene was distilled off and lower boiling materialswere distilled off at 110° C. under 0.08 mmHg to obtain 5.9 g of palebrown viscous liquid having N_(D) ²⁰ :1.5099 (yield: 98.3%).

In accordance with the same process, Compounds No. 6-1 to 6-17 were alsoproduced by using the corresponding alcohol.

PREPARATION 7-1 S-ethyl 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pententhiolate

In 70 ml of ethanol, 11.1 g (0.05 mole) of ethyl4-bromo-(2)-pententhiolate and 10.2 g (0.04 mole) of4-(4-trifluoromethylphenoxy) phenol were dissolved and 6.1 g (0.044mole) of potassium carbonate was added and the mixture was refluxed for4 hours. The reaction mixture was extracted with ether and the etherphase was washed with water and dehydrated over anhydrous sodium sulfateand ether was distilled off and lower boiling materials were distilledoff at 140° C. under 0.01 mmHg to obtain 14.7 g of an orange transparentliquid having N_(D) ²⁰ :1.5455 (yield:91.7%).

PREPARATION 7-2 S-methyl4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pententhiolate

In 100 ml of toluene, 2.9 g (0.06 mole) of methylmercaptance and 7.6 g(0.055 mole) of potassium carbonate were dissolved and 20.5 g (0.05mole) of 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoyl bromidewas added at 5° to 10° C. to react them at room temperature for 4 hours.Water was added to the reaction mixture and the toluene phase was washedwith water and dehydrated over anhydrous sodium sulfate and toluene wasdistilled off to obtain 16.7 g of an orange viscous liquid having N_(D)²⁰ :1.5502 (yield:86.9%).

In accordance with the same process, Compounds No. 7-2 to 7-9 wereproduced by using the corresponding mercaptane.

PREPARATION 8-1 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentene-1-ol

In 50 ml of dehydrated diethyl ether, 0.9 g (0.02 mole) of lithiumaluminum hydride was suspended and then a solution of 11.1 g (0.03 mole)of 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenoyl chloride in 50ml of diethyl ether was added at 5° to 10° C. under cooling with icewater. After the addition, the mixture was reacted at room temperaturefor 2 hours and excess lithium aluminum hydride was decomposed by addingethyl acetate containing water and the mixture was filtered and thefiltrate of the ether phase was washed with water and dehydrated overanhydrous sodium sulfate and ether was distilled off to obtain 8.4 g ofa pale orange viscous liquid having N_(D) ²⁰ :1.5330 (yield:82.5%).

PREPARATION 8-2 4-[4-(4-bromophenoxy)phenoxy](2)-penten-1-ol

In 50 ml of dioxane, 0.8 g (0.02 mole) of sodium boron hydride wassuspended and a solution of 7.6 g (0.02 mole) of4-[4-(4-bromophenoxy)phenoxy](2)-pentenoyl chloride in 30 ml of dioxanewas added. The mixture was reacted at room temperature for 1 hour and at45° to 50° C. for 1 hour. Acetic acid was added to the reaction mixtureto decompose excess of sodium boro hydride and the product was extractedwith ether and the ether phase was washed with water and dehydrated overanhydrous sodium sulfate and ether was distilled off to obtain 5.5 g ofa pale orange viscous liquid having N_(D) ²⁰ :1.5978 (yield:79.0%).

In accordance with the same process, Compounds No. 8-3, 4, 5 and 6 wereproduced by using the corresponding starting material.

PREPARATION 9-1 4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenylacetate

In 50 ml of acetone, 6.8 g (0.02 mole) of4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenol was dissolved and3.0 g (0.022 mole) of potassium carbonate and 1.7 g (0.022 mole) ofacetylchloride were added and the mixture was refluxed for 2 hours toreact them. The reaction mixture was cooled and poured into water andthe product was extracted with benzene and sequentially washed with 5%aqueous solution of sodium hydroxide and water and dehydrated overanhydrous sodium sulfate and benzene was distilled off and lower boilingmaterials were distilled off at 120° C. under 0.1 mmHg to obtain 6.7 gof a brown viscous liquid having N_(D) ²⁰ :1.5359 (yield:88.2%).

In accordance with the same process, Compounds No. 9-2, 3, and 4 wereproduced by using the corresponding starting compound.

PREPARATION 9-2 N-methyl4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenyl carbamate

In 50 ml of benzene, 6.8 g (0.02 mole) of4-[4-(4-trifluoromethylphenoxy)phenoxy](2)-pentenol and 1.4 g (0.025mole) of methyl isocyanate were dissolved and the mixture was stirredfor 1 hour at room temperature and then refluxed for 1 hour and thereaction product was washed with water and the benzene phase wasdehydrated over anhydrous sodium sulfate and benzene was distilled offand lower boiling materials were distilled off at 120° C. under 0.1 mmHgto obtain 7.3 g of a brown viscous liquid having N_(D) ²⁰ :1.5447(yield:92.4%).

In accordance with the same process, Compound No. 9-6 was produced byusing phenylisocyanate.

The typical compounds obtained by said processes will be exemplified.The compound numerals are referred in the following description.

    ______________________________________                                         ##STR24##                                                                    Com-                             Property                                     pound                            mp (°C.)                              No.   X      Y     A             bp (mm Hg)                                                                            N.sub.D.sup.20                       ______________________________________                                        1-1   1      H     OH            mp                                                                            152-155° C.                           1-2   I      H     OCH.sub.3             1.5619                               1-3   I      H     OC.sub.2 H.sub.5      1.5877                               1-4   I      H     OC.sub.3 H.sub.7i     1.5753                               1-5   I      H     OC.sub.4 H.sub.9sec.  1.5667                               1-6   I      H     NHC.sub.4 H.sub.9sec.                                                                       mp                                                                            165.5-                                                                        167.5° C.                             1-7   Br     H     OH            mp                                                                            140-142° C.                           1-8   Br     H     OCH.sub.3             1.5822                               1-9   Br     H     OC.sub.2 H.sub.5      1.5708                               1-10  Br     H     OC.sub.3 H.sub.7i     1.5724                               1-11  Br     H     OC.sub.4 H.sub.9sec.  1.5643                               1-12  Br     H     NHC.sub.4 H.sub.9sec.                                                                       mp                                                                            127-128° C.                           1-13  Cl     H     OH            mp                                                                            117° C.                               1-14  Cl     H     OCH.sub.3             1.5745                               1-15  Cl     H     OC.sub.2 H.sub.5      1.5514                               1-16  Cl     H     OC.sub.4 H.sub.9      1.5547                               1-17  Cl     H     OCH.sub.2 CHCH.sub.2  1.5600                               1-18  Cl     H     NH.sub.2      mp                                                                            135-137° C.                           1-19  Cl     H     N(CH.sub.3).sub.2     1.5710                               1-20  Cl     H                                                                                    ##STR25##    mp 177° C.                            1-21  Cl     H                                                                                    ##STR26##    mp 150° C.                            1-22  F      H     OC.sub.2 H.sub.5      1.6663                               1-23  Cl     Cl    OH            mp                                                                            79-81° C.                             1-24  Cl     Cl    OCH.sub.3             1.5778                               1-25  Cl     Cl    OC.sub.2 H.sub.5                                                                            bp      1.5566                                                                180-190° C.                                                            (0.007mm)                                    1-26  Cl     Cl    OC.sub.3 H.sub.7 i    1.565                                1-27  Cl     Cl    NH.sub.2      mp                                                                            105-107° C.                           2-1   Br     Cl    OCH.sub.3             1.5695                               2-2   Br     Cl    OC.sub.2 H.sub.5      1.5794                               2-3   Br     Cl    OC.sub.3 H.sub.7 i    1.5710                               2-4   Br     Cl    OCH.sub.2 CHCH.sub.2  1.5735                               2-5   Br     Cl    OCH.sub.2 CCH         1.5930                               2-6   Br     Cl    OCH.sub.2 CH.sub.2 Cl 1.5902                               3-1   Cl     Cl    ONa           mp                                                                            232-237° C.                           3-2   Cl     Cl    OFe 1/3       mp                                                                            108° C.                               3-3   Cl     H     OK            mp                                                                            244-247° C.                           3-4   Cl     H     ONH.sub.2 (CH.sub.3).sub.2                                                                  --                                           3-5   Cl     H     ONH.sub.2 (C.sub.2 H.sub.5).sub.2                                                           --                                           3-6   Br     H     OZn 1/2       mp                                                                            185-188° C.                           4-1   CF.sub.3                                                                             H     OCH.sub.2 OCH.sub.3   1.5208                               4-2   CF.sub.3                                                                             H     OCH.sub.2 CH.sub.2 OCH.sub.3                                                                        1.5156                               4-3   Cl     H     OCH.sub.2 CH.sub.2 OCH.sub.3                                                                        1.5495                               4-4   Br     H     OCH.sub.2 CH.sub.2 OCH.sub.3                                                                        1.5667                               4-5   CF.sub.3                                                                             H     OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                                 1.5134                               4-6   Br     Cl    OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                                             1.5108                               4-7   Br     Cl                                                                                   ##STR27##            1.5210                               4-8   Br     Cl                                                                                   ##STR28##            1.5110                               5-1   CF.sub.3                                                                             H     OH            mp                                                                            129-132° C.                           5-2   CF.sub.3                                                                             H     ONa           decomp                                                                        244° C.                               5-3   CF.sub.3                                                                             H     OH.NH(CH.sub. 3).sub.2                                                                      soluble                                                                       as aq.sol.                                   5-4   CF.sub.3                                                                             H     NH.sub.2      mp                                                                            140-142° C.                           5-5   CF.sub.3                                                                             H     NHCH.sub.3    mp                                                                            105-107° C.                           5-6   CF.sub.3                                                                             H     NHC.sub.3 H.sub.7                                                                           mp                                                                            111° C.                               5-7   CF.sub.3                                                                             H     N(C.sub.2 H.sub.5).sub.2                                                                    bp                                                                            190-192° C.                                                            (0.05mm)                                     5-8   CF.sub.3                                                                             H                                                                                    ##STR29##    mp 144-146° C.                        5-9   CF.sub.3                                                                             H                                                                                    ##STR30##    mp 149° C.                            5-10  CF.sub.3                                                                             H                                                                                    ##STR31##    mp 131° C.                            5-11  CF.sub.3                                                                             Cl    OH            mp                                                                            88-89° C.                             6-1   CF.sub.3                                                                             H     OCH.sub.2 CH.sub.2 CN                                                                       bp      1.5274                                                                >115° C.                                                               (0.06mm)                                     6-2   CF.sub.3                                                                             H     OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                        >115° C.                                                                       1.5178                                                                (0.095mm)                                    6-3   CF.sub.3                                                                             H     OCH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                 >130° C.                                                                       1.5139                                                                (0.15mm)                                     6-4   CF.sub.3                                                                             H     OC.sub.2 H.sub.4.O.C.sub.2 H.sub.4 OCH.sub.3                                                >110° C.                                                                       1.5168                                                                (0.06mm)                                     6-5   CF.sub.3                                                                             H     OC.sub.2 H.sub.4.O.C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                         >105° C.                                                                       1.5148                                                                (0.05mm)                                     6-6   CF.sub.3                                                                             H                                                                                    ##STR32##    >110° C. (0.05mm)                                                              1.5471                               6-7   CF.sub.3                                                                             H                                                                                    ##STR33##    >100° C. (0.04mm)                                                              1.5528                               6-8   CF.sub.3                                                                             H                                                                                    ##STR34##    >120°  C. (0.08mm)                                                             1.5439                               6-9   CF.sub.3                                                                             H                                                                                    ##STR35##    >125° C. (0.09mm)                                                              1.5459                               6-10  CF.sub.3                                                                             H                                                                                    ##STR36##    >125° C. (0.05mm)                                                              1.5528                               6-11  CF.sub.3                                                                             H                                                                                    ##STR37##    >145° C. (0.3mm)                                                               1.5461                               6-12  CF.sub.3                                                                             H                                                                                    ##STR38##    >165° C. (0.28mm)                                                              1.5430                               6-13  CF.sub.3                                                                             H                                                                                    ##STR39##    >85° C. (0.05mm)                                                               1.5472                               6-14  CF.sub.3                                                                             H                                                                                    ##STR40##    >125° C. (0.05mm)                                                              1.5503                               6-15  CF.sub.3                                                                             H                                                                                    ##STR41##    >120° C. (0.1mm)                                                               1.5574                               6-16  CF.sub.3                                                                             H                                                                                    ##STR42##    >105° C. (0.22mm)                                                              1.5240                               6-17  CF.sub. 3                                                                            H                                                                                    ##STR43##    >100° C. (0.12mm)                                                              1.5224                               6-18  CF.sub.3                                                                             H                                                                                    ##STR44##    bp >110° C. (0.08mm)                  6-19  CF.sub.3                                                                             H                                                                                    ##STR45##    >120° C. (0.05mm)                                                              1.5216                               7-1   CF.sub.3                                                                             H     SCH.sub.3             1.5522                               7-2   CF.sub.3                                                                             H     SC.sub.2 H.sub.5      1.5455                               7-3   Br     H     SC.sub.3 H.sub.7i                                          7-4   CF.sub.3                                                                             H     SC.sub.4 H.sub.9n     1.5355                               7-5   CF.sub.3                                                                             H                                                                                    ##STR46##    bp >122° C. (0.03mm)                                                           1.5870                               7-6   CF.sub.3                                                                             H                                                                                    ##STR47##    >125° C. (0.03mm)                                                              1.5962                               7-7   CF.sub.3                                                                             H                                                                                    ##STR48##    >110° C. (0.37mm)                     7-8   CF.sub.3                                                                             H                                                                                    ##STR49##    >110°  C. (0.1mm)                                                              1.5818                               7-9   CF.sub.3                                                                             H                                                                                    ##STR50##    >115° C. (0.14mm)                                                              1.5731                               ______________________________________                                         ##STR51##                                                                    Com-                             Property                                     pound                            mp (° C.)                             No.   X      Y     Z             bp (mmHg)                                                                             N.sub.D.sup.20                       ______________________________________                                        8-1   CF.sub.3                                                                             H     CH.sub.2 OH           1.5330                               8-2   Br     H     CH.sub.2 OH           1.5978                               8-3   Cl     H     CH.sub.2 OH                                                8-4   Cl     Cl    CH.sub.2 OH                                                8-5   Br     Cl    CH.sub.2 OH                                                8-6   CF.sub.3                                                                             Br    CH.sub.2 OH                                                9-1   CF.sub.3                                                                             H     CH.sub.2 OCOCH.sub.3                                                                        bp      1.5359                                                                >120° C.                                                               (0.1mm)                                      9-2   CF.sub.3                                                                             H     CH.sub.2 OCOCH.sub.2 Cl                                                                     >130° C.                                                                       1.5446                                                                (0.1mm)                                      9-3   CF.sub.3                                                                             H                                                                                    ##STR52##    >140° C. (0.1mm)                                                               1.5499                               9-4   CF.sub.3                                                                             H     CH.sub.2 OCOOC.sub.2 H.sub.5                                                                >140° C.                                                                       1.5383                                                                (0.1mm)                                      9-5   CF.sub.3                                                                             H     CH.sub.2 OCONHCH.sub.3                                                                      >120° C.                                                                       1.5447                                                                (0.1mm)                                      9-6   CF.sub.3                                                                             H                                                                                    ##STR53##    >140° C. (0.1mm)                                                               1.5548                               ______________________________________                                    

The novel compounds of the present invention produced by said syntheseshave significant herbicidal effect and non-phytotoxicity to many cropplants and can be applied to up-land, paddy fields, orchards, forestsand non-cultured grounds by the soil treatment or the foliage treatmentunder selecting suitable method of application and suitable dose of theactive ingredient.

The dose of the active ingredient of the compound of the presentinvention is depending upon a weather condition, a soil condition, aform of the composition, a season of the application and a method of theapplication and kinds of crop plants and kinds of weeds and it isusually in a range of 0.01 to 10 kg preferably 0.1 to 5 kg especially0.5 to 3 kg per 1 hectare in the treatment and it is usually applied ina concentration of 10 to 10,000 ppm preferably 100 to 5,000 ppmespecially 250 to 3,000 ppm of the active ingredient.

When the compound of the present invention is used as the herbicide, thecompound can be used in the original form and also in the form ofcompositions such as granules, wettable powder, dusts, emulsifiableconcentrates, fine power, floables, suspensions, etc to impart superioreffect.

In the preparation of the herbicidal compositions, the compound of thepresent invention can be uniformly mixed with or dissolved in suitableadjuvants such as solid carrier such as talc, bentonite, clay, kaolin,diatomaceous earth, silica gel, vermiculite, lime, siliceous sand,ammonium sulfate or urea; liquid carriers such as alcohols, dioxane,acetone, cyclohexanone, methyl naphthalene or dimethylformamide;surfactants as emulsifiers dispersing agents or wetting agents such asalkyl sulfate, alkylsulfonate, polyoxyetheyleneglycol ethers,polyoxyethylenealkylaryl ethers such as polyoxyethylenenonylphenol etheror polyoxyethylenesorbitane monoalkylate; and carboxymethyl cellulose,gum arabic and other adjuvants.

The amounts of the active ingredients, adjuvants and additives in theherbicidal compositions of the present invention will be furtherillustrated.

Wettable powder:

Active ingredient: 5 to 95 wt. % preferably 20 to 50 wt. %

Surfactant: 1 to 20 wt. % preferably 5 to 10 wt. %

Solid carrier: 5 to 85 wt. % preferably 40 to 70 wt. %

The active ingredient is admixed with the solid carrier and thesurfactant and the mixture is pulverized.

Emulsifiable concentrate:

Active ingredient: 5 to 95 wt. % preferably 20 to 70 wt. %

Surfactant: 1 to 40 wt. % preferably 5 to 20 wt. %

Liquid carrier: 5 to 90 wt. % preferably 30 to 60 wt. %

The active ingredient is dissolved in the liquid carrier and thesurfactant is admixed.

Dust:

Active ingredient: 0.5 to 10 wt. % preferably 1 to 5 wt. %

Solid carrier: 99.5 to 90 wt. % preferably 99 to 95 wt. %

The active ingredient is mixed with fine solid carrier and the mixtureis pulverized.

Granule:

Active ingredient: 0.5 to 40 wt. % preferably 2 to 10 wt. %

Solid carrier: 99.5 to 60 wt. % preferably 98 to 90 wt. %

The active ingredient is sprayed on the solid carrier or further coatedwith the solid carrier to form the granule.

The other herbicides can be incorporated in the herbicidal compositionof the present invention.

Suitable additional herbicides include; carboxylic acid type compoundssuch as 2,3,6-trichlorobenzoic acid and salts thereof,2,3,5,6-tetrachlorobenzoic acid and salts thereof,2-methoxy-3,5,6-trichlorobenzoic acid and salts thereof,2-methoxy-3,6-dichlorobenzoic acid and salts thereof,2-methyl-3,6-dichlorobenzoic acid and salts thereof,2,3-dichloro-6-methylbenzoic acid and salts thereof,2,4-dichlorophenoxyacetic acid and salts and esters thereof,2,4,5-trichlorophenoxyacetic acid and salts and esters thereof,2-methyl-4-chlorophenoxyacetic acid and salts and esters thereof,α-(2,4,5-trichlorophenoxy) propionic acid and salts and esters thereof,2-(2,4-dichlorophenoxy) butyric acid and salts and esters thereof,4-(2-methyl-4-chlorophenoxy) butyric acid and salts and esters thereof,2,3,6-trichlorophenylacetic acid and salts thereof,3,6-endoxohexahydrophthalic acid, dimethyl2,3,5,6-tetrachloroterephthalate, trichloroacetic acid and saltsthereof, 2,2-dichloropropionic acid and salts thereof and2,3-dichloroisobutyric acid and salts thereof; and carbamic acid typecompounds such as ethyl N,N-di(n-propyl) thiolcarbamate, propylN,N-di(n-propyl) thiolcarbamate, ethyl N-ethyl-N-(n-butyl)thiolcarbamate, propyl N-ethyl-N-(n-butyl) thiolcarbamate, 2-chloroallylN,N-diethyl dithiocarbamate, N-methyl dithiocarbamate, S-ethylhexahydro-1H-azepine-1-carbothioate, S-4-chlorobenzyl N,N-diethylthiolcarbamate, S-benzyl N,N-di-sec-butyl thiolcarbamate, isopropylN-phenyl carbamate, isopropyl N-(m-chlorophenyl) carbamate,4-chloro-2-butyl N-(m-chlorophenyl) carbamate, methylN-(3,4-dichlorophenyl) carbamate and methyl sulfanyl carbamate; phenoltype compounds such as dinitro-O-(sec-butyl) phenol and salts thereofand pentachlorophenol and salts thereof; urea type compounds such as3-(3,4-dichlorophenyl)-1,1-dimethyl urea, 3-phenyl-1,1-dimethyl urea,3-(3,4-dichlorophenyl)-3-methoxy-1,1-dimethylurea,3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea,3-(3,4-dichlorophenyl)-1-n-butyl-1-methylurea,3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea,3-(4-chlorophenyl)-1-methoxy-1-methylurea,3-(3,4-dichlorophenyl)-1,1,3-trimethylurea,3-(3,4-dichlorophenyl)-1,1-diethylurea,1-(2-methylcyclohexyl)-3-phenylurea,1-(5-t-butyl-1,3,4-triadiazol-2-yl)-1,3-dimethylurea,3-(3-chloro-4-methylphenyl)-1,1-dimethylurea,3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea and dichloralurea;triazine type compounds such as 2-chloro-4,6-bis(ethylamino)-s-triazine,2-chloro-4-ethylamino-6-isopropyl-amino-s-triazine,2-chloro-4,6-bis(methoxypropylamino)-s-triazine,2-methoxy-4,6-bis(isopropylamino)-s-triazine,2-methylmercapto-4,6-bis(isopropylamino)-s-triazine,2-methylmercapto-4,6-bis(ethylamino)-s-triazine,2-methylmercapto-4-ethylamino-6-isopropylamino-s-triazine,2-chloro-4,6-bis(isopropylamino)-s-triazine,2-methoxy-4,6-bis(ethylamino)-s-triazine,2-methoxy-4-ethylamino-6-isopropylamino-s-triazine,2-methylmercapto-4-(2-methoxyethylamino)-6-isopropylamino-s-triazine,2-(4-chloro-6-ethylamino-s-triazine-2-yl) amino-2-methyl propionitrile,4-amino-6-t-butyl-3-methylthio-1,2,4-triazine-5-(4H)-one, and3-cyclohexyl-6-dimethylamino-1-methyl-s-triazine-2,4-(1H, 3H) dione;ether type compounds such as 2,4-dichloro-4'-nitrodiphenyl ether,2,4,6-trichloro-4'-nitrodiphenyl ether,2,4-dichloro-6-fluoro-4'-nitrodiphenyl ether, 3-methyl-4'-nitrodiphenylether, 3,5-dimethyl-4'-nitrodiphenyl ether,2,4'-dinitro-4-trifluoromethyl diphenyl ether,2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether,2-chloro-4-trifluoromethyl-4'-nitrodiphenyl ether,2-chloro-4-trifluoromethyl-3'-ethoxy-4'-nitrodiphenyl ether,2-chloro-4-trifluoromethyl-3'-carbethoxy-4'-nitrodiphenyl ether and2-chloro-4-trifluoromethyl-3'-(1-carbethoxy) ethoxy-4'-nitrodiphenylether; anilide type compounds such as N-(3,4-dichlorophenyl)propionamide, N-(3,4-dichlorophenyl) methacrylamide,N-(3-chloro-4-methylphenyl)-2-methylpentamide,N-(3,4-dichlorophenyl)-trimethyl acetamide,N-(3,4-dichlorophenyl)-α,α-dimethyl valeramide,N-isoprophyl-N-phenylchloroacetamide,N-n-butoxymethyl-N-(2,6-diethylphenyl) chloroacetamide andN-n-methoxymethyl-N-(2,6-diethylphenyl)chloroacetamide; uracil typecompounds such as 5-bromo-3-sec-butyl-6-methyluracil,5-bromo-3-cyclohexyl-1,6-dimethyluracil,3-cyclohexyl-5,6-trimethyleneuracil, 5-bromo-3-isopropyl-6-methyluracil,and 3-tert.-butyl-5-chloro-6-methyluracil; nitrile type compounds suchas 2,6-dichlorobenzonitrile, diphenylacetonitrile,3,5-dibromo-4-hydroxybenzonitrile, and 3,5-diiodo-4-hydroxybenzonitrile;others such as 2-chloro-N,N-diallylacetamide,N-(1,1-dimethyl-2-propyl)-3,5-dichlorobenzamide, maleic acid hydrazide,3-amino- 1,2,4-triazole, mono-sodium methane arsonate, di-sodium methanearsonate, N,N-dimethyl-α,α-diphenyl acetamide,N,N-di(n-propyl)-2,6-dinitro-4-trifluoromethyl aniline,N,N-di(n-propyl)-2,6-dinitro-4-methyl aniline,N,N-di(n-propyl)-2,6-dinitro-4-methylsulfonyl aniline,O-(2,4-dichlorophenyl)-O-methylisopropyl phosphoramide thioate,4-amino-3,5,6-trichloropiclinic acid, 2,3-dichloro-1,4-naphthoquinone,dimethoxycarbonyl disulfide,3-isopropyl-1H-2,1,3-benzothiadiazine-4(3H)-one-2,2-dioxide,6,7-dihydrodipyridol [1,2-a:2':1'-c]pyrazinium salt,1,1'-dimethyl-4,4'-bipyridinium salt,3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5-thiadiazine,1,2-dimethyl-3,5-diphenylpyrazolinium methyl sulfate,N-sec-butyl-2,6-dinitro-3,4-xylidine,N-sec.-butyl-4-t-butyl-2,6-dinitroaniline, N³,N³-diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine,1,1,1-trifluoro-(4'-phenylsulfonyl)-methane sulfono-O-toluidine,2-(1-naphthoxy)-N,N-diethyl propionamide,2-t-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazoline-5-one,4-chloro-5-methylamino-2-(α,α,α-trifluoro-m-tolyl)-3(2H)-pyridazinone,N-cyclopropylmethyl-α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine andN-phosphonomethyl glycine, etc.

When the other herbicide described is mixed with the compound of thepresent invention, the ratio of the compounds and the dose of thecompounds are selected depending upon the selectivities and herbicidaleffects of the compounds to the crop plants and the control of noxiousweeds treated with them.

Certain examples of the preparation of the herbicidal compositions willbe illustrated, however, the kinds and the ratio of the adjuvants arenot limited and can be varied from the conventional consideration of theherbicidal compositions.

    ______________________________________                                        Composition No. 1: Wettable powder:                                           ______________________________________                                        Active ingredient    30 wt. %                                                 Sodium higher alcohol sulfate                                                                       5 wt. %                                                 Clay                 65 wt. %                                                 ______________________________________                                    

These components were uniformly mixed and pulverized to prepare awettable powder.

    ______________________________________                                        Composition No. 2: Emulsifiable concentrate:                                  ______________________________________                                        Active ingredient      25 wt. %                                               Polyoxyethylenealkylaryl ether                                                                       10 wt. %                                               Calcium dinaphthylmethanesulfonate                                                                    5 wt. %                                               Xylene                 60 wt. %                                               ______________________________________                                    

These components were uniformly mixed to prepare an emulsifiableconcentrate.

    ______________________________________                                        Composition No. 3: Granules:                                                  ______________________________________                                        Active ingredient   3 wt. %                                                   Bentonite          40 wt. %                                                   Clay               50 wt. %                                                   Sodium lignin sulfonate                                                                           7 wt. %                                                   ______________________________________                                    

These components were uniformly mixed and pulverized and then, kneadedwith water and granulated and dried to prepare granulates.

    ______________________________________                                        Composition No. 4: Dust:                                                      ______________________________________                                        Active ingredient                                                                               2 wt. %                                                     Clay             98 wt. %                                                     ______________________________________                                    

The components were mixed and pulverized to prepare a dust.

    ______________________________________                                        Composition No. 5: Wettable powder:                                           ______________________________________                                        Active ingredient   30 wt. %                                                  Kaolin              43 wt. %                                                  White carbon        20 wt. %                                                  Polyvinyl alcohol    5 wt. %                                                  Polyoxyethylenenonylphenol                                                                         2 wt. %                                                  ______________________________________                                    

These components were uniformly mixed and pulverized to prepare awettable powder.

    ______________________________________                                        Composition No. 6: Emulsifiable concentrate:                                  ______________________________________                                        Active ingredient   50 wt. %                                                  Polyoxyethylenenonylphenol                                                                         5 wt. %                                                  Alkylarylsulfonate   5 wt. %                                                  Xylene              40 wt. %                                                  ______________________________________                                    

These components were uniformly mixed to prepare an emulsifiableconcentrate.

    ______________________________________                                        Composition No. 7: Granules:                                                  ______________________________________                                        Active ingredient                                                                             5 wt. %                                                       Siliceous sand  92 wt. %                                                      White carbon    3 wt. %                                                       ______________________________________                                    

These components were uniformly mixed and pulverized and then, kneadedwith water and granulated and dried to prepare granulate.

    ______________________________________                                        Composition No. 8: Dust:                                                      ______________________________________                                        Active ingredient                                                                             3 wt. %                                                       White carbon    2 wt. %                                                       Kaolin          95 wt. %                                                      ______________________________________                                    

These components were mixed and pulverized to prepare a dust.

The herbicidal activity of the compounds of the present invention willbe further illustrated by certain experimental tests.

In the experiments, the following reference compounds were used ascomparative tests. ##STR54##

EXPERIMENT 1

Test for crop plants and up-land weeds in pre-emergence(pre-germination) soil treatment.

Each pot of 600 cm² was filled with up-land soil and seeds of wheat,barley, soybean, radish, barnyard grass and large crab grass were sownin a depth of 0.5 cm. Each emulsifiable concentrate prepared inaccordance with the method of Composition No. 2 was diluted with waterto give the specific concentration of the compound for the applicationof 1 Klit./ha. and the diluted solution was uniformly sprayed on thesoil surface.

Twenty days after the treatment, the herbicidal effect and thephytotoxicity of the crop plants were observed and rated as follows:

The experiments were separately carried out as stated in Tables.

    ______________________________________                                                Herbicidal effect or phytotoxicity:                                   ______________________________________                                        10:       Complete growth suppression is found;                               9:        Growth suppression of from 90 to 100%;                              8:        Growth suppression of from 80 to 90%;                               7:        Growth suppression of from 70 to 80%;                               6:        Growth suppression of from 60 to 70%;                               5:        Growth suppression of from 50 to 60%;                               4:        Growth suppression of from 40 to 50%;                               3:        Growth suppression of from 30 to 40%;                               2:        Growth suppression of from 20 to 30%;                               1:        Growth suppression of from 0 to 20%;                                0:        No herbicidal effect.                                               ______________________________________                                    

                  TABLE 1                                                         ______________________________________                                        (Test 1-1)                                                                    Results of Tests in pre-emergence soil treatments                                     Dose                                                                          active                                                                Compound                                                                              ingredient                                                            No.     (kg/ha)   Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-1 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-2 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-3 0.25      0      0    0    0    10   10                               Compound                                                                              0,5       0      0    0    0    10   10                               No. 1-4 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-5 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    8    10                               No. 1-6 0.25      0      0    0    0    4    7                                Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-7 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-8 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-9 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-10                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-11                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-12                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-13                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-14                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-15                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-16                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-17                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    9    10                               No. 1-18                                                                              0.25      0      0    0    0    5    6                                Compound                                                                              0.5       0      0    0    0    9    10                               No. 1-19                                                                              0.25      0      0    0    0    6    6                                Compound                                                                              0.5       0      0    0    0    8    9                                No. 1-20                                                                              0.25      0      0    0    0    4    6                                Compound                                                                              0.5       0      0    0    0    7    8                                No. 1-21                                                                              0.25      0      0    0    0    3    4                                Compound                                                                              0.5       0      0    0    0    8    9                                No. 1-22                                                                              0.25      0      0    0    0    7    7                                Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-23                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-24                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-25                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-26                                                                              0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 1-27                                                                              0.25      0      0    0    0    8    8                                Reference                                                                             0.5       0      0    0    0    6    6                                Compound                                                                      (I)     0.25      0      0    0    0    1    3                                ______________________________________                                         Wh.: Wheat                                                                    So.: Soybean                                                                  B.G.: Barnyard Grass (panicum crusgalli linnaeus)                             Ba.: Barley                                                                   Ra.: Radish                                                                   Cr.G.: Large Crab Grass (digitaria sanguinalis scopoli)                  

                  TABLE 2                                                         ______________________________________                                        (Test 1-2)                                                                             Dose                                                                          active                                                                        ingre-                                                               Compound dient                                                                No.      (kg/ha)  Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 0.5      0      0    0    0    10   10                               No. 2-1  0.25     0      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 2-2  0.25     0      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 2-3  0.25     0      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 2-4  0.25     0      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 2-5  0.25     0      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 2-6  0.25     0      0    0    0    10   10                               Reference                                                                              0.5      0      0    0    0    2    2                                Compound 0.25     0      0    0    0    1    1                                (II)                                                                          Reference                                                                              0.5      0      0    0    0    3    2                                Compound 0.25     0      0    0    0    0    1                                (III)                                                                         Reference                                                                              0.5      0      0    0    0    1    1                                Compound 0.25     0      0    0    0    0    0                                (IV)                                                                          Reference                                                                              0.5      0      0    0    0    0    0                                Compound 0.25     0      0    0    0    0    0                                (V)                                                                           ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        (Test 1-3)                                                                             Dose                                                                          active                                                                        ingre-                                                               Compound dient                                                                No.      (kg/ha)  Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 0.5      0      0    0    0    10   10                               No. 3-1  0.25     0      0    0    0    9    10                               Compound 0.5      0      0    0    0    10   10                               No. 3-2  0.25     0      0    0    0    9    10                               Compound 0.5      0      0    0    0    10   10                               No. 3-3  0.25     0      0    0    0    9    10                               Compound 0.5      0      0    0    0    10   10                               No. 3-4  0.25     0      0    0    0    8    10                               Compound 0.5      0      0    0    0    10   10                               No. 3-5  0.25     0      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 3-6  0.25     0      0    0    0    9    10                               Reference                                                                              0.5      0      0    0    0    4    5                                Compound 0.25     0      0    0    0    1    3                                (VI)                                                                          Reference                                                                              0.5      0      0    0    0    3    4                                Compound 0.25     0      0    0    0    1    2                                (VII)                                                                         Reference                                                                              0.5      0      0    0    0    4    4                                Compound 0.25     0      0    0    0    1    2                                (VIII)                                                                        ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        (Test 1-4)                                                                             Dose                                                                          active                                                                        ingre-                                                               Compound dient                                                                No.      (kg/ha)  Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 0.5      3      4    0    0    10   10                               No. 4-1  0.25     1      2    0    0    10   10                               Compound 0.5      4      3    0    0    10   10                               No. 4-2  0.25     1      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 4-3  0.25     0      0    0    0    10   10                               Compound 0.5      0      2    0    0    10   10                               No. 4-4  0.25     0      0    0    0    10   10                               Compound 0.5      3      4    0    0    10   10                               No. 4-5  0.25     2      2    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 4-6  0.25     0      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 4-7  0.25     0      0    0    0    10   10                               Compound 0.5      0      0    0    0    10   10                               No. 4-8  0.25     0      0    0    0    10   10                               Reference                                                                              0.5      2      4    0    0    4    3                                Compound                                                                      (IX)     0.25     0      2    0    0    0    0                                Reference                                                                              0.5      2      3    0    0    2    4                                Compound                                                                      (X)      0.25     0      2    0    0    0    1                                Reference                                                                              0.5      2      4    0    0    1    2                                Compound                                                                      (XI)     0.25     1      1    0    0    0    0                                Reference                                                                              0.5      0      2    0    0    3    4                                Compound (XII)    0.25   0    0    0    0    1                                ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        (Test 1-5)                                                                             Dose                                                                          active                                                                        ingre-                                                               Compound dient                                                                No.      (kg/ha)  Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 0.5      0      0    0    0    9    10                               No. 5-1  0.25     0      0    0    0    8    10                               Compound 0.5      0      0    0    0    10   10                               No. 5-2  0.25     0      0    0    0    9    10                               Compound 0.5      0      0    0    0    10   10                               No. 5-3  0.25     0      0    0    0    8    10                               Compound 0.5      0      0    0    0    10   10                               No. 5-4  0.25     0      0    0    0    8    10                               Compound 0.5      0      0    0    0    8    10                               No. 5-5  0.25     0      0    0    0    7    10                               Compound 0.5      0      0    0    0    8    10                               No. 5-6  0.25     0      0    0    0    7    10                               Compound 0.5      0      0    0    0    8    10                               No. 5-7  0.25     0      0    0    0    8    10                               Compound 0.5      0      0    0    0    8    7                                No. 5-8  0.25     0      0    0    0    4    5                                Compound 0.5      0      0    0    0    8    7                                No. 5-9  0.25     0      0    0    0    6    5                                Compound 0.5      0      0    0    0    8    6                                No. 5-10 0.25     0      0    0    0    6    4                                Compound 0.5      0      0    0    0    10   10                               No. 5-11 0.25     0      0    0    0    10   10                               Reference                                                                              0.5      0      0    0    0    4    5                                Compound                                                                      (I)      0.25     0      0    0    0    1    3                                ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        (Test 1-6)                                                                            Dose                                                                          active                                                                Compound                                                                              ingredient                                                            No.     (kg/ha)   Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound                                                                              0.5       6      7    0    0    10   10                               No. 6-1 0.25      3      3    0    0    10   10                               Compound                                                                              0.5       5      5    0    0    10   10                               No. 6-2 0.25      2      2    0    0    10   10                               Compound                                                                              0.5       6      6    0    0    10   10                               No. 6-3 0.25      3      3    0    0    10   10                               Compound                                                                              0.5       4      6    0    0    10   10                               No. 6-4 0.25      2      3    0    0    10   10                               Compound                                                                              6-9       3      4    0    0    10   10                               No. 6-5 0.25      1      2    0    0    10   10                               Compound                                                                              0.5       4      7    0    0    10   10                               No. 6-6 0.25      2      3    0    0    10   10                               Compound                                                                              0.5       5      6    0    0    10   10                               No. 6-7 0.25      2      3    0    0    10   10                               Compound                                                                              0.5       3      4    0    0    10   10                               No. 6-8 0.25      1      2    0    0    10   10                               Compound                                                                              0.5       7      7    0    0    10   10                               No. 6-9 0.25      3      3    0    0    10   10                               Compound                                                                              0.5       7      6    0    0    10   10                               No. 6-10                                                                              0.25      3      3    0    0    10   10                               Compound                                                                              0.5       5      4    0    0    10   10                               No. 6-11                                                                              0.25      2      2    0    0    10   10                               Compound                                                                              0.5       4      6    0    0    10   10                               No. 6-12                                                                              0.25      2      3    0    0    10   10                               Compound                                                                              0.5       7      7    0    0    10   10                               No. 6-13                                                                              0.25      3      3    0    0    10   10                               Compound                                                                              0.5       6      5    0    0    10   10                               No. 6-14                                                                              0.25      3      2    0    0    10   10                               Compound                                                                              0.5       6      4    0    0    10   10                               No. 6-15                                                                              0.25      2      1    0    0    10   10                               Compound                                                                              0.5       6      6    0    0    10   10                               No. 6-16                                                                              0.25      3      3    0    0    0    10                               Compound                                                                              0.5       6      5    0    0    10   10                               No. 6-17                                                                              0.25      3      2    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 6-18                                                                              0.25      0      0    0    0    10   10                               Reference                                                                             0.5       0      0    0    0    0    0                                Compound                                                                              0.25      0      0    0    0    0    0                                (XIII)                                                                        Reference                                                                             0.5       0      0    0    0    0    0                                Compound                                                                              0.25      0      0    0    0    0    0                                (I)                                                                           Reference                                                                             0.5       0      0    0    0    5    6                                Compound                                                                              0.25      0      0    0    0    1    2                                (VI)                                                                          Reference                                                                             0.5       0      0    0    0    4    4                                Compound                                                                              0.25      0      0    0    0    0    1                                (XIV)                                                                         Reference                                                                             0.5       2      1    0    0    10   10                               Compound                                                                              0.25      0      0    0    0    6    5                                (XV)                                                                          ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        (Test 1-7)                                                                             Dose                                                                          active                                                                        ingre-                                                               Compound dient                                                                No.      (kg/ha)  Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 0.5      10     10   0    0    10   10                               No. 7-1  0.25     10     7    0    0    10   10                               Compound 0.5      10     10   0    0    10   10                               No. 7-2  0.25     10     6    0    0    10   10                               Compound 0.5      10     10   0    0    10   10                               No. 7-3  0.25     8      5    0    0    10   10                               Compound 0.5      10     10   0    0    10   10                               No. 7-4  0.25     10     7    0    0    10   10                               Reference                                                                              0.5      2      3    0    0    2    3                                Compound                                                                      (XVI)    0.25     0      0    0    0    0    1                                Reference                                                                              0.5      0      0    0    0    0    1                                Compound                                                                      (XVII)   0.25     0      0    0    0    0    0                                ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        (Test 1-8)                                                                            Dose                                                                          active                                                                Compound                                                                              ingredient                                                            No.     (kg/ha)   Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound                                                                              0.5       0      0    0    0    10   10                               No. 8-1 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 8-2 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 8-3 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 8-4 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 8-5 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 8-6 0.25      0      0    0    0    10   10                               ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        (Test 1-9)                                                                            Dose                                                                          active                                                                Compound                                                                              ingredient                                                            No.     (kg/ha)   Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound                                                                              0.5       0      0    0    0    10   10                               No. 9-1 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 9-2 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 9-3 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 9-4 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 9-5 0.25      0      0    0    0    10   10                               Compound                                                                              0.5       0      0    0    0    10   10                               No. 9-6 0.25      0      0    0    0    10   10                               ______________________________________                                    

EXPERIMENT 2

Test for crop plants and up-land weeds in pre-emergence soil treatment.

Each polyethylene pot of 2,000 cm² was filled with up-land soil andseeds of rice, maize, wheat, soybean, cotton, radish, barnyard grass,large crab grass, dent foxtail, johnson grass and goose foot (25 seedsfor each plant) were sown in a depth of 0.5 cm.

Each emulsifiable concentrate prepared in accordance with the method ofComposition No. 2 was diluted with water to give 0.25, 0.125 and 0.625Kg/ha. of the active ingredient, and the diluted solution was uniformlysprayed on the surface of the soil at a rate of 20.0 ml per one pot.

Twenty days after the treatment, the herbicidal effect and thephytotoxicity of the crop plants were observed and rated as describedabove.

    ______________________________________                                        Ric.:   Rice                                                                  Mai.:   Maize                                                                 Wh.:    Wheat                                                                 So.:    Soybean                                                               Cot.:   Cotton                                                                Ra.:    Radish                                                                B.G.:   Barnyard Grass (panicum crus-galli linnaeus)                          Cr.G.:  Large Crab Grass (digitaria sanguinalis scopoli)                      D.F.:   Dent Foxtail (alopecurus aequalis sobolewski var.                             amurensis ohwi)                                                       J.G.:   Johnson Grass (sorghum halepense)                                     G.F.:   Goose Foot (chenopodium album linnaeus var.                                   centrorubrum makino)                                                  ______________________________________                                    

The experiments were separately carried out as stated in Tables.

                                      TABLE 10                                    __________________________________________________________________________     (Test 2-1)                                                                             Dose                                                                          active                                                              Compound  ingredient                                                          No.       (kg/ha)                                                                             Ric.                                                                             Mai.                                                                             Wh.                                                                              So.                                                                              Cot.                                                                             Ra.                                                                              B.G.                                                                             Cr.G.                                                                             D.F.                                                                             J.G.                                                                             G.F.                           __________________________________________________________________________    Compound  0.25  6  4  0  0  0  0  10 10  10 10 0                              No. 1-3   0.125 4  1  0  0  0  0  8  10  10 10 0                                        0.0625                                                                              1  0  0  0  0  0  6  7   8  8  0                              Compound  0.25  7  5  0  0  0  0  10 10  10 10 0                              No. 1-8   0.125 5  1  0  0  0  0  9  9   10 10 0                                        0.0625                                                                              2  0  0  0  0  0  6  7   9  7  0                              Compound  0.25  6  4  0  0  0  0  10 10  10 10 0                              No. 1-9   0.125 4  1  0  0  0  0  9  10  10 10 0                                        0.0625                                                                              2  0  0  0  0  0  7  7   8  8  0                              Compound  0.25  5  3  0  0  0  0  10 10  10 10 0                              No. 1-10  0.125 4  1  0  0  0  0  8  9   9  10 0                                        0.0625                                                                              1  0  0  0  0  0  6  7   9  9  0                              Compound  0.25  4  3  0  0  0  0  10 10  10 10 0                              No. 1-15  0.125 2  0  0  0  0  0  7  8   10 8  0                                        0.0625                                                                              0  0  0  0  0  0  5  6   8  8  0                              Compound  0.25  6  4  0  0  0  0  10 10  10 10 0                              No. 1-24  0.125 4  1  0  0  0  0  9  9   10 10 0                                        0.0625                                                                              1  0  0  0  0  0  7  7   8  8  0                              Compound  0.25  6  4  0  0  0  0  10 10  10 10 0                              No. 1-25  0.125 4  1  0  0  0  0  8  9   10 9  0                                        0.0625                                                                              2  0  0  0  0  0  6  6   9  7  0                              Compound  0.25  5  3  0  0  0  0  10 10  10 10 0                              No. 1-26  0.125 3  1  0  0  0  0  8  8   9  9  0                                        0.0625                                                                              1  0  0  0  0  0  6  6   7  7  0                              Reference 0.25  0  0  0  0  0  0  2  3   2  0  0                              Compound (XXIII)                                                                        0.125 0  0  0  0  0  0  0  0   0  0  0                                        0.0625                                                                              0  0  0  0  0  0  0  0   0  0  0                              Reference 0.25  0  0  0  0  0  0  1  2   1  0  0                              Compound (XXIV)                                                                         0.125 0  0  0  0  0  0  0  0   0  0  0                                        0.0625                                                                              0  0  0  0  0  0  0  0   0  0  0                              __________________________________________________________________________

                                      TABLE 11                                    __________________________________________________________________________    (Test 2-2)                                                                            Dose                                                                          active                                                                Compound                                                                              ingredient                                                            No.     (kg/ha)                                                                             Ric.                                                                             Mai.                                                                             Wh.                                                                              So.                                                                              Cot.                                                                             Ra.                                                                              B.G.                                                                             Cr.G.                                                                             D.F.                                                                             J.G.                                                                             G.F.                             __________________________________________________________________________    Compound                                                                              0.25  3  4  0  0  0  0  10 10  10 10 0                                No. 2-1 0.125 0  0  0  0  0  0  10 10  10 9  0                                Compound                                                                              0.25  3  4  0  0  0  0  10 10  10 10 0                                No. 2-2 0.125 0  0  0  0  0  0  10 10  10 10 0                                Compound                                                                              0.25  3  3  0  0  0  0  10 10  10 10 0                                No. 2-3 0.125 0  0  0  0  0  0  10 10  10 8  0                                Compound                                                                              0.25  3  3  0  0  0  0  10 10  10 10 0                                No. 2-4 0.125 0  0  0  0  0  0  10 9   10 9  0                                Compound                                                                              0.25  3  3  0  0  0  0  10 10  10 10 0                                No. 2-5 0.125 0  0  0  0  0  0  10 8   9  7  0                                Compound                                                                              0.25  3  3  0  0  0  0  10 10  10 10 0                                No. 2-6 0.125 0  0  0  0  0  0  10 10  9  7  0                                Reference                                                                             0.25  2  3  0  0  0  0  6  4   3  2  0                                Compound (II)                                                                         0.125 1  0  0  0  0  0  1  0   0  0  0                                Reference                                                                             0.25  2  4  0  0  0  0  5  5   4  1  0                                Compound (III)                                                                        0.125 0  1  0  0  0  0  0  2   1  0  0                                Reference                                                                             0.25  2  3  0  0  0  0  3  4   5  2  0                                Compound (IV)                                                                         0.125 0  1  0  0  0  0  0  0   1  0  0                                Reference                                                                             0.25  3  3  0  0  0  0  1  2   4  1  0                                Compound (V)                                                                          0.125 0  0  0  0  0  0  0  0   0  0  0                                __________________________________________________________________________

                                      TABLE 12                                    __________________________________________________________________________    (Test 2-3                                                                             Dose active                                                           Compound                                                                              ingredient                                                            No.     (kg/ha)                                                                             Ric.                                                                             Mai.                                                                             Wh.                                                                              So.                                                                              Cot.                                                                             Ra.                                                                              B.G.                                                                             Cr.G.                                                                             D.F.                                                                             J.G.                                                                             G.F.                             __________________________________________________________________________    Compound                                                                              0.25  5  8  3  0  0  0  10 10  10 10 0                                No. 4-1 0.125 3  6  2  0  0  0  10 10  10 10 0                                        0.0625                                                                              0  2  0  0  0  0  10 10  10 7  0                                Compound                                                                              0.25  6  8  3  0  0  0  10 10  10 10 0                                No. 4-2 0.125 3  7  1  0  0  0  10 10  10 10 0                                        0.0625                                                                              0  3  0  0  0  0  10 10  10 5  0                                Compound                                                                              0.25  2  3  0  0  0  0  10 10  10 10 0                                No. 4-3 0.125 0  0  0  0  0  0  10 10  10 10 0                                        0.0625                                                                              0  0  0  0  0  0  10 10  10 6  0                                Compound                                                                              0.25  1  1  0  0  0  0  10 10  10 10 0                                No. 4-4  0.125                                                                              0  0  0  0  0  0  10 10  10 10 0                                        0.0625                                                                              0  0  0  0  0  0  10 10  10 8  0                                Compound                                                                              0.25  6  7  3  0  0  0  10 10  10 10 0                                No. 4-5 0.125 2  5  1  0  0  0  10 10  10 9  0                                        0.0625                                                                              0  1  0  0  0  0  7  8   7  7  0                                Compound                                                                              0.25  1  1  0  0  0  0  10 10  10 10 0                                No. 4-6 0.125 0  0  0  0  0  0  10 10  10 10 0                                        0.0625                                                                              0  0  0  0  0  0  8  7   7  6  0                                Compound                                                                              0.25  1  1  0  0  0  0  10 10  10 10 0                                No. 4-7 0.125 0  0  0  0  0  0  10 10  10 10 0                                        0.0625                                                                              0  0  0  0  0  0  7  10  8  6  0                                Compound                                                                              0.25  0  1  0  0  0  0  10 10  10 10 0                                No. 4-8 0.125 0  0  0  0  0  0  10 10  10 10 0                                        0.0625                                                                              0  0  0  0  0  0  10 10  8  6  0                                Reference                                                                             0.25  0  0  0  0  0  0  1  3   2  1  0                                Compound (IX)                                                                         0.125 0  0  0  0  0  0  0  1   0  0  0                                        0.0625                                                                              0  0  0  0  0  0  0  0   0  0  0                                Reference                                                                             0.25  0  0  0  0  0  0  0  0   2  0  0                                Compound (XI)                                                                         0.125 0  0  0  0  0  0  0  0   0  0  0                                        0.0625                                                                              0  0  0  0  0  0  0  0   0  0  0                                __________________________________________________________________________

EXPERIMENT 3

Test for crop plants and up-land weeds in (post-emergence germination)foliage treatment.

Each pot of 600 cm² was filled with up-land soil and seeds of corn,barley, soybean, radish, barnyard grass and large crab grass were sown.

Each emulsifiable concentrate prepared in accordance with the method ofComposition No. 2 was diluted with water to give the specificconcentration of the compound and the diluted solution was uniformlysprayed at a rate of 1 kl/ha, when the gramineous weeds were grown to 2to 2.5 leaf stage and the broad-leaf weeds were grown to the firstdivergence stage.

Fifteen days from the treatment, the herbicidal effect and thephytotoxicity of the crop plants were observed and rated as describedabove.

    ______________________________________                                        Wh.:     Wheat                                                                Ba.:     Barley                                                               So.:     Soybean                                                              Ra.:     Radish                                                               B.G.:    Barnyard Grass (panicum crus-galli linnaeus)                         Cr.G.:   Large Crab Grass (digitaria sanguinalis scopoli)                     ______________________________________                                    

The experiments were separately carried out as stated in Tables.

                  TABLE 13                                                        ______________________________________                                        (Test 3-1)                                                                             Concen-                                                              Compound tration                                                              No.      (ppm)    Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 500      0      0    0    0    10   10                               No. 1-1  200      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-2  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-3  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-4  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-5  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    8    7                                No. 1-6  250      0      0    0    0    5    5                                Compound 500      0      0    0    0    10   10                               No. 1-7  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-8  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-9  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-10 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-11 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-12 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-13 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-14 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-15 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-16 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-17 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    7    7                                No. 1-18 250      0      0    0    0    4    5                                Compound 500      0      0    0    0    7    7                                No. 1-19 250      0      0    0    0    4    5                                Compound 500      0      0    0    0    7    6                                No. 1-20 250      0      0    0    0    3    4                                Compound 500      0      0    0    0    7    6                                No. 1-21 250      0      0    0    0    3    4                                Compound 500      0      0    0    0    7    7                                No. 1-22 250      0      0    0    0    6    6                                Compound 500      0      0    0    0    10   10                               No. 1-23 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-24 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-25 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-26 250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 1-27 250      0      0    0    0    7    6                                Reference                                                                     Compound 500      0      0    0    0    4    5                                (I)      250      0      0    0    0    1    2                                ______________________________________                                    

                  TABLE 14                                                        ______________________________________                                        (Test 3-2)                                                                             Concen-                                                              Compound tration                                                              No.      (ppm)    Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 500      0      0    0    0    10   10                               No. 2-1  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 2-2  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 2-3  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 2-4  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 2-5  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 2-6  250      0      0    0    0    10   10                               Reference                                                                              500      0      0    0    0    4    2                                Compound 250      0      0    0    0    1    1                                (II)                                                                          Reference                                                                              500      0      0    0    0    2    0                                Compound 250      0      0    0    0    0    0                                (III)                                                                         Reference                                                                              500      0      0    0    0    4    2                                Compound 250      0      0    0    0    1    0                                (IV)                                                                          Reference                                                                              500      0      0    0    0    0    0                                Compound 250      0      0    0    0    0    0                                (V)                                                                           ______________________________________                                         The diluted solution was applied when the gramineous weeds were grown to      3.0 to 3.5 leaf stage.                                                        The other conditions were the same.                                      

                  TABLE 15                                                        ______________________________________                                        (Test 3-3)                                                                             Concen-                                                              Compound tration                                                              No.      (ppm)    Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 500      2      2    0    0    10   10                               No. 4-1  250      0      1    0    0    10   10                               Compound 500      10     9    0    0    10   10                               No. 4-2  250      6      8    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 4-3  250      0      0    0    0    10   10                               Compound 500      0      1    0    0    10   10                               No. 4-4  250      0      0    0    0    10   10                               Compound 500      4      6    0    0    10   10                               No. 4-5  250      3      4    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 4-6  250      0      0    0    0    9    10                               Compound 500      0      0    0    0    10   10                               No. 4-7  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 4-8  250      0      0    0    0    10   9                                Reference                                                                              500      0      0    0    0    2    3                                Compound 250      0      0    0    0    0    0                                (IX)                                                                          Reference                                                                              500      0      0    0    0    3    4                                Compound 250      0      0    0    0    1    2                                (X)                                                                           Reference                                                                              500      0      0    0    0    0    0                                Compound 250      0      0    0    0    0    0                                (XI)                                                                          Reference                                                                              500      0      0    0    0    1    2                                Compound 250      0      0    0    0    0    0                                (XII)                                                                         ______________________________________                                         The diluted solution was applied when the gramineous weeds were grown to      3.0 to 3.5 leaf stage.                                                        The other conditions were the same.                                      

                  TABLE 16                                                        ______________________________________                                        (Test 3-4)                                                                             Concen-                                                              Compound tration                                                              No.      (ppm)    Wh.    Ba.  So.  Ra.  B.G. Cr.G.                            ______________________________________                                        Compound 500      0      0    0    0    10   10                               No. 8-1  250      0      0    0    0    10   10                               Compound 500      0      0    0    0    10   10                               No. 8-2  250      0      0    0    0    10   10                               Reference                                                                     Compound                                                                      500      8        9      0    0    9    8                                     (XVIII)  250      6      7    0    0    7    6                                Reference                                                                     Compound 500      7      8    0    0    9    8                                (XIX)    250      4      6    0    0    7    6                                Reference                                                                     Compound 500      9      10   0    0    10   8                                (XX)     250      7      6    0    0    7    5                                Reference                                                                     Compound 500      8      9    0    0    10   10                               (XXI)    250      5      6    0    0    7    6                                Reference                                                                     Compound 500      7      7    0    0    10   10                               (XXII)   250      5      5    0    0    8    7                                ______________________________________                                    

EXPERIMENT 4

Test for crop plants and up-land weeds in post-emergence foliagetreatment.

Each polyethylene pot of 2,000 cm² was filled with up-land soil andseeds of rice, maize, wheat, soybean, cotton, radish, barn-yard grass,crab grass, dent foxtail, johnson grass and goose foot (25 seeds foreach plant) were sown.

Each emulsifiable concentrate prepared in accordance with the method ofComposition No. 2 was diluted with water to give the concentration of125, 62.5 and 31.25 ppm and the diluted solution was uniformly sprayedat a rate of 20.0 ml per pot, when the plants were grown to 2 to 4 leafstages.

Ten days from the treatment, the herbicidal effect and the phytotoxicityof the crop plants were observed and rated as described above.

    ______________________________________                                        Ric:   Rice                                                                   Mai.:  Maize                                                                  Wh.:   Wheat                                                                  So.:   Soybean                                                                Cot.:  Cotton                                                                 Ra.:   Radish                                                                 B.G.:  Barnyard Grass (panicum crus-galli linnaeus)                           Cr.G.: Large Crab Grass (digitaria sanguinalis scopoli)                       D.F.:  Dent Foxtail (alopecurus aequalis sobolewski var.                             amurensis ohwi)                                                        J.G.:  Johnson Grass (sorghum halepense)                                      G.F.:  Goose Foot (chenopodium album linnaeus var.                                   centrorubrum makino)                                                   ______________________________________                                    

In Test 4-2, twenty days from the treatment, the herbicidal effect andthe phytotoxicity of the crop plants were observed.

                                      TABLE 17                                    __________________________________________________________________________    (Test 4-1)                                                                          Concen-                                                                 Compound                                                                            tration                                                                 No.   (ppm)                                                                              Ric.                                                                             Mai.                                                                             Wh.                                                                              So.                                                                              Cot.                                                                             Ra.                                                                              B.G.                                                                             Cr.G.                                                                             D.F.                                                                             J.G.                                                                             G.F.                                __________________________________________________________________________    Compound                                                                            125  3  0  0  0  0  0  10 10  10 10 0                                   No. 1-3                                                                             62.5 0  0  0  0  0  0  10 10  10 10 0                                         31.25                                                                              0  0  0  0  0  0  6  8   9  8  0                                   Compound                                                                            125  6  5  0  0  0  0  10 10  10 10 0                                   No. 1-8                                                                             62.5 2  2  0  0  0  0  10 10  10 10 0                                         31.25                                                                              0  0  0  0  0  0  8  10  10 9  0                                   Compound                                                                            125  6  5  0  0  0  0  10 10  10 10 0                                   No. 1-9                                                                             62.5 2  2  0  0  0  0  10 10  10 10 0                                         31.25                                                                              0  0  0  0  0  0  9  10  9  9  0                                   Compound                                                                            125  5  5  0  0  0  0  10 10  10 10 0                                   No. 1-10                                                                            62.5 1  1  0  0  0  0  10 10  10 10 0                                         31.25                                                                              0  0  0  0  0  0  8  10  9  9  0                                   Compound                                                                            125  4  3  0  0  0  0  10 10  10 10 0                                   No. 1-15                                                                            62.5 0  0  0  0  0  0  8  8   8  8  0                                         31.25                                                                              0  0  0  0  0  0  5  6   6  7  0                                   Compound                                                                            125  0  4  0  0  0  0  10 10  10 8  0                                   No. 1-24                                                                            62.5 0  1  0  0  0  0  10 9   8  7  0                                         31.25                                                                              0  0  0  0  0  0  7  8   7  6  0                                   Compound                                                                            125  0  4  0  0  0  0  10 10  10 8  0                                   No. 1-25                                                                            62.5 0  1  0  0  0  0  10 9   8  7  0                                         31.25                                                                              0  0  0  0  0  0  8  7   0  5  0                                   Compound                                                                            125  0  3  0  0  0  0  10 10  10 8  0                                   No. 1-26                                                                            62.5 0  1  0  0  0  0  10 8   7  7  0                                         31.25                                                                              0  0  0  0  0  0  7  7   6  6  0                                   Reference                                                                           125  0  0  0  0  0  0  0  0   0  0  0                                   Compound                                                                            62.5 0  0  0  0  0  0  0  0   0  0  0                                   (XXIII)                                                                             31.25                                                                              0  0  0  0  0  0  0  0   0  0  0                                   Reference                                                                           125  0  0  0  0  0  0  0  0   0  0  0                                   Compound                                                                            62.5 0  0  0  0  0  0  0  0   0  0  0                                   (XXIV)                                                                              31.25                                                                              0  0  0  0  0  0  0  0   0  0  0                                   __________________________________________________________________________

                                      TABLE 18                                    __________________________________________________________________________    (Test 4-2)                                                                          Concen-                                                                 Compound                                                                            tration                                                                 No.   (ppm)                                                                              Ric.                                                                             Mai.                                                                             Wh.                                                                              So.                                                                              Cot.                                                                             Ra.                                                                              B.G.                                                                             Cr.G.                                                                             D.G.                                                                             J.G.                                                                             G.F.                                __________________________________________________________________________    Compound                                                                            125  7  8  0  0  0  0  10 10  10 10 0                                   No. 2-1                                                                             62.5 1  3  0  0  0  0  10 10  10 10 0                                   Compound                                                                            125  7  8  0  0  0  0  10 10  10 10 0                                   No. 2-2                                                                             62.5 2  3  0  0  0  0  10 10  10 10 0                                   Compound                                                                            125  7  7  0  0  0  0  10 10  10 10 0                                   No. 2-3                                                                             62.5 2  2  0  0  0  0  10 10  10 10 0                                   Compound                                                                            125  6  3  0  0  0  0  10 10  10 10 0                                   No. 2-4                                                                             62.5 0  0  0  0  0  0  10 10  10 10 0                                   Compound                                                                            125  5  2  0  0  0  0  10 10  10 10 0                                   No. 2-5                                                                             62.5 0  0  0  0  0  0  10 10  10 10 0                                   Compound                                                                            125  5  2  0  0  0  0  10 10  10 10 0                                   No. 2-6                                                                             62.5 0  0  0  0  0  0  10 10  10 10 0                                   __________________________________________________________________________

                                      TABLE 19                                    __________________________________________________________________________    (Test 4-3)                                                                              Concen-                                                             Compound  tration                                                             No.       (ppm)                                                                              Ric.                                                                             Mai.                                                                             Wh.                                                                              So.                                                                              Cot.                                                                             Ra.                                                                              B.G.                                                                             Cr.G.                                                                             D.G.                                                                             J.G.                               __________________________________________________________________________    Compound  125  3  2  0  0  0  0  10 10  10 10                                 No. 8-1   62.5 0  0  0  0  0  0  10 10  10 10                                           31.25                                                                              0  0  0  0  0  0  10 10  10 10                                 Compound  125  2  1  0  0  0  0  10 10  10 10                                 No. 8-2   62.5 0  0  0  0  0  0  10 10  10 10                                           31.25                                                                              0  0  0  0  0  0  10 10  10 10                                 Reference 125  5  4  3  0  0  0  7  4   6  1                                  Compound (XVIII)                                                                        62.5 2  2  2  0  0  0  2  0   3  0                                            31.25                                                                              0  0  1  0  0  0  0  0   0  0                                  Reference 125  7  2  3  0  0  0  7  6   5  4                                  Compound (XIX)                                                                          62.5 3  0  1  0  0  0  3  4   3  0                                            31.25                                                                              1  0  0  0  0  0  0  0   0  0                                  Reference 125  4  2  4  0  0  0  6  5   5  4                                  Compound (XX)                                                                           62.5 1  0  2  0  0  0  2  2   1  1                                            31.25                                                                              0  0  0  0  0  0  0  0   0  0                                  Reference 125  5  3  3  0  0  0  6  6   5  5                                  Compound (XXI)                                                                          62.5 2  1  1  0  0  0  4  2   4  2                                            31.25                                                                              0  0  0  0  0  0  1  0   0  1                                  Reference 125  4  2  3  0  0  0  7  6   6  6                                  Compound (XXII)                                                                         62.5 1  1  0  0  0  0  4  3   4  2                                            31.25                                                                              0  0  0  0  0  0  0  0   1  1                                  __________________________________________________________________________

What is claimed is:
 1. Phenoxyphenoxy unsaturated derivative having theformula ##STR55## wherein X represents a halogen atom or CF₃ ; Yrepresents a hydrogen atom or a halogen atom; and Z represents --COOR,--COR", --CH₂ OH or --CH₂ OR"' and R represents cyanoethyl,dialkylaminoethyl, alkoxyalkyl, benzyl, dialkylbenzyl, alkylbenzyl,halobenzyl, pyridinomethyl, furfuryl, cycloalkyl, methylcycloalkyl,phenyl, halophenyl, methyl phenyl, alkoxy alkyleneoxy alkyl,methoxymethylbutyl group, a metal atom, amino, alkylamino or arylaminogroup; and when X is a halogen atom, R can be an alkyl, haloalkyl,alkenyl, haloalkenyl, alkynyl or hydrogen atom group; and R" representsa hydrogen atom, amino, alkylamino, dialkylamino, phenylamino orphenylamino group which may be substituted by halo or alkyl group, andR"' represents an acetyl, chloroacetyl, benzoyl, ethoxycarbonyl,methylcarbamoyl or phenylcarbamoyl group.
 2. Phenoxyphenoxy unsaturatedderivatives according to claim 1 which are phenoxyphenoxy unsaturatedderivatives having the formula ##STR56## wherein X, Y and R are definedabove.
 3. Phenoxyphenoxy unsaturated derivatives according to claim 1which are phenoxyphenoxy unsaturated derivatives having the formula##STR57## wherein X and Y are defined above.
 4. Phenoxyphenoxyunsaturated derivatives according to claim 1 which are phenoxyphenoxyunsaturated derivatives having the formula ##STR58## wherein X, Y andR"' are defined above.
 5. A herbicidal composition which comprises aphenoxyphenoxy unsaturated derivative having the formula ##STR59##wherein X represents a halogen atom or CF₃ ; Y represents a hydrogenatom or a halogen atom; and Z represents --COOR, --COR", --COOH, --CH₂OH or --CH₂ OR'" and R represents cyanoethyl, dialkylaminoethyl,alkoxyalkyl, benzyl, dialkylbenzyl, alkylbenzyl, halobenzyl,pyridinomethyl, furfuryl, cycloalkyl, methylcyloalkyl, phenyl,halophenyl, methyl phenyl, alkoxy alkyleneoxy alkyl, methoxymethylbutylgroup, a metal atom, amino, alkylamino or arylamino group; and when X isa halogen atom, R can be an alkyl, haloalkyl, alkenyl, haloalkenyl,alkynyl or hydrogen atom group; and R" represents, amino, alkylamino,dialkylamino, phenylamino or phenylamino group which may be substitutedby halo or alkyl group, and R"' represents an acetyl, chloroacetyl,benzoyl, ethoxycarbonyl, methylcarbamoyl or phenylcarbamoyl group.
 6. Aherbicidal composition according to claim 5 wherein the compound (I) isa phenoxyphenoxy unsaturated derivative having the formula ##STR60## 7.A herbicidal composition according to claim 5 wherein the compound (I)is a phenoxyphenoxy unsaturated derivative having the formula ##STR61##8. A method of treating plants with a herbicide, comprising:applying aherbicidally effective amount of the herbicidal composition of claim 5to the soil or the foliage of plants.
 9. A method of treating plantswith a herbicide, comprising:applying an amount of the composition ofclaim 5 to the soil such that from 0.01 to 10 kg of the activeingredient of said composition is applied per 1 ha. of soil
 10. A methodof treating plants with a herbicide, comprising:applying the compositionof claim 5 diluted to an active ingredient concentration of 10 to 10,000ppm to the foilage of plants.